Process for the production of 2-hydroxyalkylthiolcarbonates



United States Patent 3,335,161 PROCESS FOR THE PRODUCTION OF 2-HY- DROXYALKYLTHIOLCARBONATES Donald L. Fields and Delbert D. Reynolds, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Original application June 9, 1961, Ser. No. 115,932, now Patent No. 3,221,013, dated Nov. 30, 1965. Divided and this application Aug. 29, 1963, Ser. No. 308,922.

6 Claims. (Cl. 260-455) This application is a division of our application Ser. No. 115,932, filed June 9, 1961, and entitled, New Mercaptoethylating Agents, which issued as US. Patent No. 3,221,013 on Nov. 30, 1965.

This invention concerns a process for reacting mercaptoethylating reagents with primary and secondary amines to introduce the mercaptoethyl radical into amines in order to prepare aminoethanethiols, and a process for preparing an advantageous intermediate for use in the reaction.

Mercaptans and their derivatives are useful in many applications, for example, in the rubber industry, as disclosed by H. R. Snyder et al., J. Amer. Chem. Soc., 69, 2672 (1947), in the pharmaceutical field as disclosed by R. 0. Clinton et al., J. Amer. Chem. Soc., 70, 950 (1948), and in the photographic industry in photographic emulsions and the like.

Among the mercaptans one highly useful class is the mercaptoethyl derivatives, in particular the aminoethanethiols derived from primary and secondary amines, and having the general formula RRNCH CH SH, where R and R are hydrogen, alkyl, aryl or aralkyl. Three methods have customarily been used to synthesize these compounds. One involves the reaction of aminoethyl halides with hydrosulfides of the alkali metals. Another is based on the condensation of aminoethyl halides with thiourea followed by alkaline hydrolysis. A third and more preferred method is the mercaptoethylation of primary and secondary amines by reaction with ethylene sulfide. This last process leaves much to be desired because of the difficulties encountered in handling ethylene sulfide. Ethylene sulfide readily polymerizes and cannot be stored safely in large quantities. Hence this process is not suitable for mercaptoethylation on a large scale.

Aminoethanethiols are valuable compounds. They are useful as antiradiation drugs. This family of compounds had shown the capacity to protect animal tissues against radiation. This use of aminoethanethiols is described in Chem. and Eng. News, Nov. 23, 1959, pp. 42-53. The aminoethanethiols of our invention may be used in photography for various purposes. As shown hereinafter they may be advantageously utilized as unique fixing agents to fix silver halide emulsion layers subsequent to development in order to stabilize the silver image.

One object of this invention is to obtain aminoethanethiols by the mercaptoethylation of primary or secondary amines. Another object is to provide a mercaptoethylation process which avoids the difiiculties inherent in using ethylene sulfide due to its inclination to polymerize. An additional object is to obtain mercaptoethyl derivatives.

A further object is to provide reactions employing 2-hydroxyethylthiolcarbonate esters and Z-mercaptoethylcarbonate esters for providing useful compounds. An additional object is to obtain useful compound by reacting 2-hydroxyethylthiolcarbonate esters and 2-mercaptoethylcarbonate esters with primary and secondary amines. Another object of this invention is to provide a process for the preparation of 2-hydroxyethylthiolcarbonate esters.

In carrying out our invention to produce an aminoethanethiol, we treat a primary or secondary amine with a compound of the generic formula,

ROCOACH CH B (Q) in which A and B are dissimilar and may be selected from the class consisting of sulfur and oxygen. R may be alkyl (methyl through octyl), aryl (phenyl and phenyl substituted with methyl through butyl groups) or aralkyl. Q may be hydrogen, -COR, CO R, CONHR, or CONR where R is defined as above. This reaction can be called mercaptoethylation of an amine.

Any amine with a replaceable hydrogen atom attached to the amino nitrogen is operative in this process. Thus the reagent ROCOACH CH B(Q) may be reacted with any primary or secondary amine which is aliphatic, aromatic, or cyclic. When the amine reactant is aromatic it is preferable to have present a catalytic amount of a base such as sodium methoxide. Diamines are operable as long as at least one of its amine functions has the abovementioned labile hydrogen atom.

In general, any amino function in the presence of other non-participating functions, for example, polyamines, polymines, amino acids, polypeptides, proteins, amino sugars, deacetylated chitin, gelatin, and the like, can be mercaptoethylated with the mercaptoethylating agents of our invention.

In carrying out our invention, we prepare representative compounds which fit into the generic formula. The first compounds are as follows: 2-hydroxyethylthiolcarbonate esters. Referring to the above generic formula, A=sulfur; R=alkyl (methyl through octyl), aryl, or aralkyl; B=oxygen; Q=hydrogen, COR, CO R, CONHR, or CONR (R is defined as above). The preferred members of this group of compounds are those wherein Q is hydrogen.

Alkyl, aralkyl or aryl 2-hydroxyalkylthiolcarbonates may be prepared by reacting alkyl, aralkyl or aryl chloroformate with 2-mercaptoalkanols, such as Z-mercaptoethanol, 3-mercapto-l, 2-propanediol, 1-mercapto-2-propanol, 1-mercapto-2-butanol, l-mercapto-Z-hexanol, 1- mercapto-Z-heptanol, l-mercapto-Z-decanol, and the like, in the presence of an inorganic basic material which converts the mercaptoethanol to a mercaptide of an alkali or alkaline earth metal. Suitable reagents are thealkali metal bases such as sodium hydroxide, potassium hydroxide, or lithium hydroxide. The reaction is preferably carried out at a pH of 6 to 8, but may be varied. A twophase solvent system is used employing Water and an immiscible inactive solvent, such as benzene, ethyl ether, petroleum ether, or the like.

In our preferred embodiment, the reaction to obtain ethyl Z-hydroxyethylthiolcarbonate may be run continuously by reacting an aqueous solution of sodium 2-hydroxyethylmercaptide with a benzene solution of ethyl chloroformate by introducing the reactants simultaneously through a series of mixing reactors followed by distillation of the final product. The following formula indicates the reaction:

Potassium hydroxide or lithium hydroxide may be substituted for sodium hydroxide in the reaction. Other chloroformates :may be used such as aryl chloroformates, aralkyl or alkyl chloroformates employing alkyl groups of 1 to 8 carbon atoms. The alkyl chloroforrnates are preferred.

Z-mercaptoethylcarbonate esters, Referring to the previously-mentioned generic formula: A=oxygen; R=alkyl (methyl through octyl), aryl, or aralkyl; B=sulfur; Q: hydrogen, -COR, -CO R, CONHR, or CONR (R is defined as above). The preferred members of this group are those wherein Q is hydrogen.

Alkyl, aralkyl or aryl Z-mercaptoethylcarbonates may be prepared by reacting alkyl, aralkyl or aryl chloroformate with 2-mercaptoethanols, such as 2-mercapto-, ethanol, 3mercapto-l,2-propanediol, l-mercapto-Z-propanol, l-mercapto-Z-butanol, l-mercapto-Z-hexanol, l-mercapto-2-heptanol, 1-mercapto-2-decanol, and the like, in a nonbasic medium. The reaction is preferably carried out at a pH below 6, but may be varied. The product may be isolated by fractional distillation.

The yields of 2-mercaptoethylcarbonate ester obtained in the chloroformate-nonbasic medium reaction are low. Improved yields of the Z-mercaptoethylcarbonate esters are obtained by converting the 2-hydroxyethylthiolcarbonate esters by an isomerization process in the presence of certain catalysts. This process is described in detail in Johnson and Reynolds copending application, Ser. No. 80,970, filed Jan. 6, 1961, abandoned but continued in part in pending Johnson and Reynolds US. application Ser. No. 388,295, filed Aug. 7, 1964.

In reactions known to those skilled in the art, the group of compounds defined as ROCOACH CH BH may be converted to 1 ROCOACH CH BCOR 2) ROCOACH CH BCO R (3 ROCOACH CH CONHR and (4) ROCOACH CH CONR by treating said BH compound with various reactants, respectively (1) acyl halides, (2) chloroformate esters (chlorocarbonates), (3) isocyanates, and (4) carbamoyl halides.

The following examples are intended to illustrate our invention and not to limit it in any way:

EXAMPLE 1 Preparation of ethyl Z-hydrbxyethylthiolcarbonate A mixture of one liter of benzene, 542 g. (5 moles) of ethyl chloroformate and 200 m1. of water was stirred at 15 C. A solution consisting of 1.5 l. of water, 200 g. (5 moles) of sodium hydroxide and 390 g. (5 moles) of 2- mercaptoethanol was added over a period of one hour. During this time, the reaction temperature was maintained between 15 and 20 C. After stirring for an additional 15 minutes, the reaction mixture was acidified With hydrochloric acid. The benzene layer was separated, washed once with 500 ml. of cold water, separated and dried over anhydrous MgSO Twenty-five grams of stearic acid was added and the benzene removed under vacuum. The ethyl Z-hydroxyethylthiolcarbonate was then distilled through an 18" glass-helices-packed column equipped with a variable reflux rate stillhead. B.P. 84 C./0.4 mm.; n 1.4782; yield 653 g. (87 percent).

4 EXAMPLE 2 The following procedure is for a seven-hour run of a continuous reactor for the preparation of ethyl 2-hydroxyethylthiolcarbonate.

Three liters of ice and water were stirred while 800 g. (20 mole) of sodium hydroxide pellets were added in portions. To this cooled solution were added 1562 g. (20 moles) of 2-mercaptoethanol in portions. The resulting solution was diluted with water to a total of 5.7 liters. This solution was transferred to a reservoir. Two thousand one hundred and sixty g. (20 moles) of ethylchloroformate were diluted with stirring to 5.7 l. with benzene, then transferred to a second reservoir. The levels of the solutions in the two reservoirs were kept constant by adding additional quantities of the above solutions as required.

The reservoirs are connected to a reaction flask by pumps. The reaction flask is connected in series by Tygon tubing with three additional flasks, the flasks arranged in a cascade system with thefirst flask at the greatest height above the reservoirs.

With the pumps adjusted to deliver the reactants from each of the two reservoirs at the rate of 19 moles per hour and the reaction flasks equipped with stirrers and half-filled with water, the pumps were turned on. The two reservoir solutions were pumped into the highest flask where, under stirring, the two-phase reaction was commenced. As the first reaction flask filled to the level of the Tygon tubing, the partially completed reaction mixture overflowed (cascaded) to the next flask, and so on, until the completed reaction mixture collected in the final receiver.

Each three liters of benzene product solution from the final receiver was washed with 500 ml. water and 3 ml. concentrated hydrochloric acid. Stearic acid (20 g. per 3 l. of solution) was added to insure acid conditions during the subsequent distillation step. Benzene and residual water were removed azeotropically under reduced pressure. Product isolation was effected through a 14" glass-helices-packed column.

Seven hours operation of the reactor produced 18.25 kg. or 91.6 percent of ethyl 2-hydroxyethylthiolcarbonate, B.P. 110 C., 11 1.4782.

Analysis.Calcd. for C d-1 0 8: C, 40.0; H, 6.7; S, 21.3. Found: C, 40.3; H, 6.7; S, 21.1.

EXAMPLE .3

n-Hexyl Z-hydroxyethylthiolcarbonate To a vigorously stirred solution of 823 g. (5 moles) nhexyl chloroformate in three liters of benzene, were added slowly with cooling a solution of 200 g. (5 moles) sodium hydroxide and 390 g. (5 moles) of Z-mercaptoethanol in three liters of watenThe reaction mixture was stirred an additional hour, acidified with hydrochloric acid,

and the organic layer distilled through a 14" packed column. n-Hexyl Z-hydroxyethylthiolcarbonate (B.P. 109

C./0.05 mm., refractive index 1.4718) was obtained in 77.4 percent yield.

EXAMPLE 4 Phenyl 2hydroxyethylthiolcarbonate EXAMPLE '5 Isobutyl 2hydroxyethylthiolcarbonale Isobntyl 2-hydroxyethylthiolcarbonate was prepared by the procedure of Example 1 in percent yield from isobutyl chloroformate and sodium Z-hydroxyethylmercaptide on a 3.7 mole basis. The reaction was considerably more sluggish than in the preparation of ethyl 2-hydroxyethylthiolcarbonate, necessitating a 4-hour mercaptide addition period at 40 C. The product had a B.P. of 5 81 C./0.1 mm., n 1.4696 and gave a negative I mercaptan test.

Analysis.Calcd. for C'7H14O3SI C, 47.2; H, 7.8; S, 18.0. Found: C, 47.0; H, 7.9; S, 17.8.

EXAMPLE 6 Preparation of ethyl Z-mercaptoethylcarbonate 2-mercaptoethanol 6 g., 2.0 moles) and ethyl chloroformate (434 g., 4.0 moles) were heated on a steam bath 1 under a reflux condenser for seven hours. Crude ethyl 2- mercaptoethylcarbonate was collected by distillation, B.P. 74-80 C./7.0 mm, n 1.4568. Yield, 105 g. percent).

placed under vacuum and distilled, producing 85 g. or 82 percent yield of-n-hexyl Z-mercaptoethylcarbonate (B.P. 75 C./ 0.2 mm., refractive index 1.4542, 99.5 percent pure by iodornetric tritation).

Similarly, aryl Z-mercaptoethylcarbonates may be obtained by isomerizing aryl 2-hydroxyethylthiolcarbonates.

EXAMPLE 8 Mercaptoethylation with alkyl Z-hydroxyethylthiolcarbonates TABLE I B.P. range, Percent yield Amine Product C./mm. of aminov ethanethlol Piperidine 2-piperidinoethanethiol 81-87/12 62 4-methylp1pen'd1ne-. 2-(4-ruethylpiperidino)ethanethlol 101-104/12 59 Morpholine 2-morpholinoethanethi0l 107-111/26 62 Diethylamine 2dlethylaminoethauethiol 73-74/34 61 Di-n-butylamin 2-di-n-butylaminoethanethiol 64/0.7 73 n-Hexylamine 2-n-hexylaminoethanethiol 114-130/15 46 TABLE II B.P. range, Percent yield Amine Product C./mm. n1, of aminoethanethiol Piperidine 2-piperldinoethanethiol 88-91/15 1.4985 61 Morpholine 2-morpholinoethanethio1 109-114/24 1.5014 57 Di-n-butylamin 2-di-n-butylaminoethanethiol. 64/0.7 1.4619 69 n-Hexylamme 2-n-l1exylam noethanethiol 6365/0.7 1.4691 46 Analysis.-Calcd. for C H O S: C, 40.0; H, 6.7; S, EXAMPLE 9 21.3. Found: C, 40.2; H, 6.7; S, 21.3.

EXAMPLE 7 n-Hexyl Z-mercaptoethylcarbonate n-Hexyl Z-mercaptoethylcarbonate was prepared in a ZOO-m1. flask equipped with a 14" packed column, and a variable-rate still-head. In the flask was placed 103 g. (0.5 mole) of n-hexyl 2-hydroxyethylthiolcarbonate (Example 3) and 0.002 g. of uranyl acetate. The system was Mercaptoethylation with alkyl 2-mercapt0ethylcarb0nates General procedure: A mixture of amine (3.0 moles) and anhydrous toluene (500 ml.) was brought to reflux under an efiicient condenser topped by an acetone-Dry Ice helices-packed column equipped with a variable take-011.

head.

TABLE III 1 RNH1+EtOCO CH, CH: SH RNHCH: CH2 SH+C0a+EtOH Analysis, Percent Percent Percent B.P., N0. RNH- Yield Purity fl C./mm. 11,1 Calculated Found C H N C H N iso-CaH NH 7 82.2 56/18 50.4 10.9 11.8 51.0 10.8 11.2

n-C4H9NH 32 98. 2 76/13 1. 4694 iso-C4H9NH- 37 94.2 79/23 1. 4645 54.1 11.3 10.5 53.8 11.4 10.6 Se0-C4H9NH 42 95.8 74/21 1.4670 54.1 11.3 10.5 54.2 11.3 10.4 te1t-G4HQNH 15 92.4 29 54.1 11.3 10.5 54.3 10.5 10.5 CHFCHOHzNH- 44 94.9 70/16 1.4931 51.3 9.4 12.0 51.5 9.1 12.9

n-C5H13NH-- 66 99.0 97/7 1. 4680 ll-C8H17NH 64 98.5 83/03 14591 53.5 12.2 7.4 04.0 12.5 7.3 D-O10H21NH- 68 97.8 /06 1.4674 66.4 12.4 6.5 66.0 12.2 6.6

O5H5CH2NH- 72 100.0 84/0. 1 1. 5585 CsHnNH- 65 98.0 99/7 1.5040 60.4 10.7 8.8 60.3 10.7 8.6

l Purity determined by iodometn'e titration.

TABLE IV RqNH+EtOCO2CH2OHzSH RaNCHzOHzSH-l-OOz-l-EtOI-I Analysis, Percent Percent Percent No. RzN- Yield Purity .P., nu Calculated Found C./mm

C H N C H N (O2H5)2B-- 73 100.0 85/56 O3H'/)Z 88 98.8 77/10 (1SO'O3H7)2N'' 10 95. 7 73/9 (n-C4H9)2N 91 100. 66/0. 7 (is0-C4Ho)zN-- 89 100.0 91/10 (see-C4H9)2N 20 95. 93/8 -C5H11)2N 90 100. 0 91/0. 8 (iSO'C5H1l)2 92 99.6 85/1 (CH7=OHCH2)2N- 92 90/17 12 CH N N- 94 100.0 95/10 1. 5040 B Determined by iodometric titration.

With diarnines, for example piperazine, the mercaptoethylation is carried out in a similar manner. 2.2 moles of ethyl 2-mercaptoethylcarbonate and one mole of diamine (piperazine) were treated as above. In this case the product, N,-N'-piperazinebis(ethanethiol). (compound N0. 13, Table IV) was isolated by distillation through an 8" Vigreux column.

The results are tabulated in Tables III and IV.

EXAMPLE Since many amines have low boiling points, very low reaction temperatures are obtained at normal pressure. With aromatic amines a basic catalyst, such as sodium methoxide, is used. By conducting the reaction in a rocking-type autoclave, employing a positive displacement pump to meter the 2-hydroxyethylthiolcarbonate ester or the Z-mercaptoethylcarbouate ester into the amine-solvent mixture, yields can be significantly improved because of the higher operating temperature.

General. mercaptoethylation procedure for amines of Table V A charge consisting of amine (3.0 mole) and benzene (150 ml.) Was loaded into a stainless steel autoclave. The autoclave was sealed, placed in a rocking heater stand and heated to 125-150 C. Agitation was started at this point and ethyl Z-mercaptoethylcarbonate (150 g., 1.0 mole) was metered into the autoclave by means of a Lapp Pulsafeeder metering pump. This addition required approximately 15 min., and was followed by 50 ml. of benzene. Agitation was continued for 5-10 111111., at the operating temperature with the final pressure reaching 500-1500 p.s.i. depending on the vapor pressure of the amine used.

The autoclave was removed from the heater stand, cooled to room temperature, vented in a hood, and the product isolated by distillation through a 14" glasshelices-packed column equipped with a variable takeoff head. Invsorne instances the mixture from the autoclave contained a considerable amount of solid carbamate salt 9 09 (RZNO O2R2NH2) This material, however, was usually heat unstablev and it decomposed into its components (amine. and CO before the distillation of the desired product commenced.

General mercaptoethylation procedure for aromatic amines of Table VI A mixture consisting of the aromatic amine (3.0 mole), ethyl Z-mercaptoethylcarbonate (1.50 g., 1.0 mole), benzene (150 ml.) and sodium methoxide (1.0 g.) was charged into a stainless steel autoclave. The autoclave was sealed and heated with agitation for one to three hours at 125-150. After cooling, the mixture was removed from the autoclave and isolation of the product was efiected by distillation through a 14" Vigreux column equipped with variable take-01f head.

A'nal.--Calcd. for 0 1111 NOS: 0, 39.7; H, 9.1; N, 11.6. Found: C 39.4; H, 8.6; N, 11.5.

b AnaL-Calcd. for 0 15113 NOS: 0, 44.4; H, 9.6; N, 10.4. Found: C 44.7; H, 9.6; N, 10.2.

Purity determined by iodometric titration.

d IVLP. 34-35" C.

TABLE VI No. R Yield B.P., n3

CJmm.

CoH5- 81 /0. 5 1. 6022 p-OHaCaH4- 86 91/0. 02 1. 5867 p-CHaO CsHr- 78 /0. 02 1. 5914 p-ClCeHr- 67 112/0. 02 1. 6127 9 EXAMPLE 11 ROCOACH CH B(Q) is prepared as follows:

amino substituent, such as mercaptoacetic acid, require alkaline conditions for fixing.

R A B Q S H Example 6. O S H Replace ethyl chloroi'ormate of Example 6 with methyl chloroformate; or the isomerization reaction analogous to Example 7. O S H Replace ethyl chloroformate of Example 6 with phenyl chloroformate. O S H ce ethyl chloroiormate of Example 6 with propyl chloroformate. O S H Replace ethyl chloroformate of Example 6 with isopropyl chloroformate. O S H Replace ethyl chloroiormate of Example 6 with n-butyl chloroformate. G O S H Replace ethyl chloroformate of Example 6 with lsobutyl chloroformate. H. CH3(CH2)4 O S H Replace ethyl chloroformate of Example 6 with n-pentyl chloroformate. I CHa(CHz) 0 S H Replace ethyl chloroionnate of Example 6 with n-hexyl chloroformate; or Example J (A) through (I) O S COR; R is alkyl or aryl Compounds (A) through (I) reacted with any acyl chloride or acid anhydride. K. do 0 S 00 R; R is (A) through (I) Compounds (A) through (I) reacted with alkali and reacted with the chloroformates corresponding to the R of (A) through (I). L S CONHR; R is alkyl or aryl.-. Compounds (A) through (I) reacted with alkyl or aryl isocyanate (RNCO).

S CON R2; NR is: Compounds (A) through (I) reacted with carbamoyl chloride (RzNCOCl). (CH3)2N- The carbomoyl chloride is obtained from 1 mol phosgene reacted with 1 mol of the corresponding secondary amine (RgNH). N-

CHaNC 0H5 CHsCHzNCsHs CH (CH2)2CHzNCaH5 (CC a 2)4CH2NCu t 6 5 (pCH CaH4)2N N CHQCHT- S O H Example 1 or 2. O H3 S 0 H Replace ethyl chloroformate of Example 1 with methyl chloroformate. P CaH5 S O H Example 4. Q.. CHa(CHz)z S O H Replace ethyl chloroformate of Example 1 with propyl chloroformate. R". (C 3);;CH S O H Replace ethyl chloroformate of Example 1 with isopropyl chloroformate. S CH;(CH)i- S 0 H Replace ethyl chloroformate in Example 1 with butyl chloroformate. '1 (OHa)2CHCHz S 0 H Example 5. U CH3(CH;)4 S O H Replace ethyl chloroformate of Example 1 with n-pentyl chloroformate. V CH3(CH;)5- S O H Example 3. W. (N) through (V) S O COR; R 1s alkyl or aryl Compounds (N) through (V) reacted with any acyl chloride or acid anhydride. X. do S O 0 0: These compounds are identical to those of K. Y do S O CONHR: R is alkyl or aryl Compounds (N) through (V) reacted with alkyl or aryl isocyanate. Z do s O OONRr; NR1 is: Compounds (N) through (V) reacted with carbamoyl chloride (R NOOOl). (0H3)2N The carbamoyl chloride is obtained from 1 mol phosgene reacted with 1 mol of the corresponding secondary amine (RzNH). c.

CH3NCBH5 CHaCHgNCtHE C s( z)2 2 Cc 5 CH:(OH2)4CH2NC5H5 CeHa zN-- (ID-CH3 C eH4)2N The amines which may be used in our invention are not limited to any particular number of carbon atoms providing they are primary or secondary amines. The amines which are operative include all types of primary and secondary amines including aliphatic, aromatic, and cyclic amines.

The reactants can be dissolved in suitable inert common solvents, such as toluene, dioXane, xylene, benzene, di-n-butyl ether, halogenated hydrocarbons, and the like, and heated to the reflux temperature of the solvent used.

The aminoethanethiols of this invention may be used in photography for various purposes. For example, it is well known in photography to fix silver halide emulsion layers subsequent to development in order to stabilize the silver image. Instead of this procedure the aminoethanethiols may be applied to the developed print in vapor form, for example, from a boiling aqueous solution, with the result that a stable silver complex is formed. This procedure obviates the usual fixing and Washing steps. However, the aminoethanethiols may be used in solutions for fixing prints in the usual manner, in which case they form soluble salts with the residual silver halide which can be readily Washed out of the print. The solutions may further contain organic colloid hardening agents such as aluminum formoacetate, glutaraldehyde and potassium alum. The aminothiols will dissolve silver hallide in acid solution whereas thiols lacking an Our process of mercapt-oethylating amines has many advantages over other systems of mercaptoethylating. We have already pointed out the advantages over the systems known in the prior art.

One of us has previously discovered an improved process of mercaptoethylating amines by reaction with a certain amount of ethylene monothiolcarbonate, Reynolds Ser. 721,678, filed Mar. 17, 1958 (abandoned).

Our present invention discloses an even more advantageous over-all process for effecting the desired mercaptoethylations, The 2-hydroxyethylthiocarbonate esters of our present invention are the intermediate chemicals for preparing ethylene monothi-olcarbonate, as disclosed in Johnson and Fields, Ser. No. 73,183, filed Dec. 2, 1960, issued Jan. 8, 1963 as U.S. Patent No. 3,072,676. Hence, in economic terms, mercaptoethylating with Z-hydroxyethylthiolcarbonate esters is equivalent to effecting the over-all set of reactions in one less step.

The Z-mercaptoethyl carbonate esters are the preferred embodiment of our present invention. In the described process of mercaptoethylating amines, these agents are the preferred mercaptoethylating agents and eflect the conversion of amines to aminoethanethiols with the highest yields. In the mercaptoethylation process the 2-mercaptoethylcarbonate esters may be considered the equivalent of the 2-hydroxyethylthiolcarbonate esters since, by the isomerization of Example 3 and more fully described 11 in Ser. No. 80,970 (above), the 2-hydroxyethylthiolcarbonates can be converted to Z-mercaptoethylcarbonate esters.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected Within the spirit and scope of the invention described hereinabove and as defined in the appended claims.

We claim:

1. The process which comprises contacting a 2-mercaptoalkanol having 2 to about carbon atoms with a chloroformate selected from the group consisting of alkyl chloroformates, the alkyl moiety of which contains up to about 8 carbon atoms, phenylchlorofonnate in the presence of an alkali metal base; said contacting being carried out in a two-phase liquid solvent system comprising water and an inert, water-immiscible organic solvent; and obtaining a 2-hydroxyalkylthiolcanbonate ester.

2. The process which comprises contacting a 2-rnercaptoalkanol having 2 to about 10 carbon atoms with an alkyl chloroformate, the alkyl moiety of which contains up to about 8 carbon atoms, in the presence of an alkali metal base; said contacting being carried out in a twophase, liquid solvent system comprising water and an inert, water-immiscible organic solvent; and obtaining an alkyl 2-hydroXyalkylthiolcarbonate.

3. The process which comprises contacting 2-mercapt-oethanol with ethylchloroformate in the presence of sodium hydroxide; said contacting being carried out in a two-phase, liquid solvent system comprising water and benzene; and obtaining ethyl 2-hydroxyethylthiolcarbonate.

4. The process which comprises contacting 2-mercaptoethanol with n-hexyl chloroformate in the presence of sodium hydroxide; said contacting being carried out in a two-phase, liquid solvent system comprising water and benzene; andobtaining n-hexyl Z-hydroxyethylthiolcarbonate.

5. The process which comprises contacting Z-mercaptoethanol with phenyl chloroformate in the presence of sodium hydroxide; said contacting being carried out in a two-phase, liquid solvent system comprising water and benzene; and obtaining phenyl 2-hydroxyethylthiolcarbonate.

6. The process which comprises contacting 2-mercaptoethanol with isobutyl chloroformate in the presence of sodium hydroxide; said contacting being carried out in a two-phase, liquid solvent system comprising water and benzene; and obtaining isobutyl 2-hydroxyethylthiocarbonate.

References Cited UNITED STATES PATENTS 2/1945 Muskat et a1. 260463 OTHER REFERENCES CHARLES B. PARKER, Primary Examiner.

JOSEPH P. BRUST, Examiner.

D. R. MAHANAND, D. R. PHILLIPS,

Assistant Examiners. 

1. THE PROCESS WHICH COMPRISES CONTACTING A 2-MERCAPTOALKANOL HAVING 2 TO ABOUT 10 CARBON ATOMS WITH A CHLOROFORMATE SELECTED FROM THE GROUP CONSISTING OF ALKYL CHLOROFORMATES, THE ALKYL MOIETY F WHICH CONTAINS UP TO ABOUT 8 CARBON ATOMS, PHENYLCHLOROFORMATE IN THE PRESENCE OF AN ALKALI METAL BASE; SAID CONTACTING BEING CARRIED OUT IN A TWO-PHASE LIQUID SOLVENT SYSTME COMPRISING WATER AND AN INERT, WATER-IMMISCIBLE ORGANIC SOLVENT; AND OBTAINING A 2-HYDROXYALKYLTHIOLCARBONATE ESTER. 